EP3872036A1 - Système de synthèse d'ammoniac et procédé de production d'ammoniac - Google Patents
Système de synthèse d'ammoniac et procédé de production d'ammoniac Download PDFInfo
- Publication number
- EP3872036A1 EP3872036A1 EP19876356.7A EP19876356A EP3872036A1 EP 3872036 A1 EP3872036 A1 EP 3872036A1 EP 19876356 A EP19876356 A EP 19876356A EP 3872036 A1 EP3872036 A1 EP 3872036A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ammonia
- gas
- containing gas
- ammonia synthesis
- circulated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 1682
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 805
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 371
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 261
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 96
- 239000007789 gas Substances 0.000 claims abstract description 474
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 151
- 239000003054 catalyst Substances 0.000 claims abstract description 138
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 109
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 83
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 238000001816 cooling Methods 0.000 claims description 92
- 238000000034 method Methods 0.000 claims description 20
- 230000006835 compression Effects 0.000 claims description 14
- 238000007906 compression Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 description 84
- 239000002184 metal Substances 0.000 description 84
- 150000001875 compounds Chemical class 0.000 description 47
- 239000011575 calcium Substances 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000012495 reaction gas Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- 238000004088 simulation Methods 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 11
- 150000001408 amides Chemical class 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- 239000002131 composite material Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- -1 O2- Chemical class 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 229910000765 intermetallic Inorganic materials 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 229910052707 ruthenium Inorganic materials 0.000 description 9
- 229910052712 strontium Inorganic materials 0.000 description 9
- 229910052723 transition metal Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 229910052788 barium Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000737 periodic effect Effects 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical group 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052747 lanthanoid Inorganic materials 0.000 description 4
- 150000002602 lanthanoids Chemical class 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000009620 Haber process Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229910052790 beryllium Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0458—Separation of NH3
- C01C1/047—Separation of NH3 by condensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/245—Stationary reactors without moving elements inside placed in series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to an ammonia synthesis system for synthesizing ammonia from nitrogen gas and hydrogen gas and a method for producing ammonia.
- Nitrogenous fertilizers such as ammonium sulfate and urea, which are widely used in agricultural production, are produced using ammonia as a main raw material.
- ammonia is considered as a very important chemical material and a method for producing ammonia has been studied.
- the Haber-Bosch Process is a method for producing ammonia by bringing nitrogen and hydrogen as raw materials into contact with a catalyst containing iron as a main component under a high temperature and a high pressure.
- PTL 1 discloses an ammonia synthesis system in which ammonia gas containing unreacted gases is cooled to a temperature of 30 to 50°C with a water cooling-type or air cooling-type cooler in extracting the product ammonia as liquid.
- the pressure of the ammonia gas in cooling is to be increased.
- the reaction pressure in the ammonia synthesis is 7 to 25 MPa, and more preferably 10 to 20 MPa.
- a reaction pressure exceeding 10 MPa is needed (see paragraph [0033] in PTL 1, 13.8 MPa in Examples).
- the energy required for cooling the ammonia gas is reduced, there is a problem in that the energy required for increasing the reaction pressure in ammonia synthesis is even increased and thus the total energy required for producing ammonia is not largely reduced.
- the energy required for cooling the ammonia gas is, for example, an energy for driving a cooler for cooling the ammonia gas
- the energy required for increasing the reaction pressure in ammonia synthesis is, for example, an energy for driving a gas compressor used for compressing gas.
- the present invention has an object to provide an ammonia synthesis system and an ammonia production method in which an energy required for producing ammonia can be reduced while securing the ability to produce ammonia.
- the present inventors have found that the above object can be achieved by using a reaction pressure in ammonia synthesis of a prescribed value or less and an ammonia gas concentration in a circulated gas used for the ammonia synthesis of a prescribed value or more, completing the present invention.
- the present invention is as follows.
- the present invention can provide an ammonia synthesis system and an ammonia production method in which the energy required for producing ammonia can be reduced while securing the ability to produce ammonia.
- Fig. 1 is a schematic view illustrating an ammonia synthesis system according to an embodiment of the present invention.
- An ammonia synthesis system 1 of an embodiment of the present invention includes: an ammonia synthesis reaction unit 10 that includes two ammonia synthesis reactors 11 and 12 that synthesize ammonia from nitrogen and hydrogen using an ammonia synthesis catalyst; an ammonia cooler 20 that cools an ammonia-containing gas (NH 3 -containing gas) which is discharged from the ammonia synthesis reaction unit 10 and which contains ammonia gas synthesized in the ammonia synthesis reaction unit 10; a gas-liquid separator 30 that separates liquefied ammonia which is produced from the ammonia-containing gas cooled by the ammonia cooler 20 from a circulated gas which contains unreacted nitrogen gas, unreacted hydrogen gas, and ammonia gas; and an ammonia synthesizing gas supplying unit 40 that supplies nitrogen gas and hydrogen gas to be added to the circulated gas. Then, the circulated gas having added thereto the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supplying unit 40 is supplied to the ammonia synthesis reaction
- the ammonia synthesis system 1 in an embodiment of the present invention may further include, as desired, an ammonia synthesizing gas compressor 50 that compresses the nitrogen gas and hydrogen gas supplied from the ammonia synthesizing gas supplying unit 40 and a circulated gas compressor 60 that compresses the circulated gas separated by the gas-liquid separator 30.
- an ammonia synthesizing gas compressor 50 that compresses the nitrogen gas and hydrogen gas supplied from the ammonia synthesizing gas supplying unit 40
- a circulated gas compressor 60 that compresses the circulated gas separated by the gas-liquid separator 30.
- the ammonia synthesis reaction unit 10 includes the two ammonia synthesis reactors 11 and 12 that synthesize ammonia from nitrogen and hydrogen using an ammonia synthesis catalyst. Then, the circulated gas having added thereto the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supplying unit 40 is supplied to the ammonia synthesis reaction unit 10.
- the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12 is not particularly limited as long as it is an ammonia synthesis catalyst that is capable of synthesizing ammonia from nitrogen and hydrogen at a reaction pressure of 10 MPa or less.
- the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12 is preferably a catalyst that has a high activity even at a high ammonia concentration.
- ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12 examples include (i) a supported metal catalyst prepared using a conductive mayenite compound as a carrier, (ii) a supported metal catalyst prepared using a two-dimensional electride compound or a precursor compound thereof as a carrier, and (iii) a supported metal catalyst prepared using a composite of a carrier substrate and a metal amide supported on the carrier substrate as a carrier, the carrier substrate containing at least one metal oxide selected from ZrO 2 , TiO 2 , CeO 2 , and MgO, the metal amide being represented by the formula M(NH 2 ) x (wherein M represents at least one selected from Li, Na, K, Be, Mg, Ca, Sr, Ba and Eu and x represents the valence of M).
- the "conductive mayenite compound" used as a carrier of the supported metal catalyst is a mayenite compound containing conductive electrons.
- the mayenite compound refers to a composite oxide having a crystal structure of the same type as the crystal structure of the mineral mayenite itself, the mayenite rock, and the mineral mayenite crystal.
- the crystal of a mayenite compound is composed of cages with an inner diameter of about 0.4 nm that are linked in a three-dimensional manner with the walls shared with one another.
- a negative ion such as O 2-
- O 2- is contained inside each cage of the mayenite compound, and the negative ion can be replaced with a conductive electron through annealing. By increasing the annealing time, the conductive electron concentration in the mayenite compound is increased.
- a representative composition of the conductive mayenite compound is represented by the formula [Ca 24 Al 28 O 64 ] 4+ (O 2- ) 2-x (e - ) 2x (0 ⁇ x ⁇ 2).
- the conductive electron concentration in the mayenite compound is preferably 10 15 cm -3 or more, more preferably 10 16 cm -3 or more, further preferably 10 17 cm -3 or more, and furthermore preferably 10 18 cm -3 or more.
- the upper limit of the conductive electron concentration is not particularly limited, and may typically be 2.2 ⁇ 10 21 cm -3 or less, or 2.0 ⁇ 10 21 cm -3 or less, for example.
- the conductive electron concentration in the mayenite compound can be measured, for example, by the method described in WO 2012/077658 .
- a part or all of Ca contained in the formula of the representative composition may be replaced with at least one typical metal element or transition metal element selected from the group consisting of Li, Na, K, Mg, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ir, Ru, Rh, and Pt.
- a part or all of Al contained in the representative composition may be replaced with at least one typical metal element or transition metal element selected from the group consisting of B, Ga, C, Si, Fe, and Ge.
- a part or all of O contained in the formula of the representative composition may be replaced with at least one typical element or metal element selected from the group consisting of H, F, Cl, Br, and Au.
- the conductive mayenite compound can be prepared, for example, by a method described in WO 2012/077658 .
- the conductive mayenite compound may be an electride of a conductive mayenite compound.
- An example of the conductive mayenite compound is an electride of a mixed oxide of calcium and aluminum (electride of 12CaO ⁇ 7Al 2 O 3 ).
- the "two-dimensional electride compound" used as a carrier of the supported metal catalyst refers to a layered compound in which electrons are present as anions between layers, in other words, an electride in which layers are connected via electrons present between the layers.
- electrons are present in a spatial gap as two-dimensionally delocalized anionic electrons.
- the electrons can quite smoothly move throughout the compound.
- Ca 2 N is a two-dimensional electride ( K. Lee, S. W. Kim, Y. Toda, S. Matsuishi, and H. Hosono, "Nature”, Vol. 494, pp. 336-341 (2013 )).
- Ca 2 N is a layered compound in which an electron is bound as an anion between layers composed of [Ca 2 N] + , and can be obtained by heating Ca 3 N 2 and metal Ca in vacuum. It is reported that Ca 2 N has a conductive electron concentration of 1.39 ⁇ 10 22 cm -3 and a work function of 2.6 eV. Subsequently, A. Walsh and D. O. Scanlon reports the two-dimensional electride in Journal of Materials Chemistry C, Vol.
- a nitride electride containing a nitride having a layered crystal structure and represented by an ionic formula [AE 2 N] + e - (AE is at least one element selected from Ca, Sr, and Ba) is reported ( JP 2014-24712 A ).
- Examples of the two-dimensional electride compound that can be used as a carrier of a supported metal catalyst include at least one selected from the group consisting of a nitride electride represented by the formula M 1 2 N (wherein M 1 represents at least one selected from the group consisting of Ca, Sr, and Ba) and a carbide electride represented by the formula M 2 2 C (wherein M 2 represents at least one selected from the group consisting of Y, Sc, Gd, Tb, Dy, Ho, and Er). Note that a part of M 1 and M 2 may be replaced with at least one alkali metal element selected from the group consisting of Li, Na, K, Rb, and Cs.
- a precursor compound of the two-dimensional electride compound may also be used as a carrier.
- Ca 2 N which is a two-dimensional electride compound
- Ca-N-H compound As the hydrogenated calcium nitride (hereinafter "Ca-N-H compound”), Ca 2 NH, CaNH, Ca(NH 2 ) 2 , and the like are known.
- Precursor compounds of Sr 2 N or Ba 2 N are similar to the precursor compounds of Ca 2 N.
- the precursor compound of the two-dimensional electride compound is at least one selected from the group consisting of a nitride represented by the formula M 1 3 N 2 and a compound represented by the formula M 1 x N y H z (1 ⁇ x ⁇ 11, 1 ⁇ y ⁇ 8, 0 ⁇ z ⁇ 4).
- M 1 represents at least one selected from the group consisting of Ca, Sr, and Ba.
- the two-dimensional electride compound may be prepared by a known method.
- Ca 2 N can be obtained by mixing Ca 3 N 2 and metal Ca and heating the mixture under a vacuum condition for a long time (for example, at a temperature as high as about 800°C for about 100 hours).
- ammonia synthesis activity is dramatically increased to achieve a catalyst having significantly high performance that is stable even in a long-time reaction.
- a carrier of the supported metal catalyst a composite of a carrier substrate and a metal amide supported on the carrier substrate, the carrier substrate containing at least one metal oxide selected from ZrO 2 , TiO 2 , CeO 2 , and MgO, the metal amide being represented by the formula M(NH 2 ) x (wherein M is at least one selected from Li, Na, K, Be, Mg, Ca, Sr, Ba, Yb, and Eu), is also suitably used.
- Ca(NH 2 ) 2 when Ca(NH 2 ) 2 is used as a metal amide, Ca(NH 2 ) 2 is converted to Ca 2 N or a Ca-N-H compound, such as Ca 2 NH or CaNH, under an ammonia synthesis condition, and cooperates with an active metal to increase the function as an active species.
- the supported metal catalyst containing the composite as a carrier can achieve a stable catalytic activity for a long time in ammonia synthesis.
- a carrier substrate activated charcoal, graphite, a metal oxide, and the like can be used, and a carrier substrate having a basic to neutral surface, such as ZrO 2 , TiO 2 , CeO 2 , and MgO, is preferred.
- a carrier substrate containing one or more thereof may be used.
- the carrier substrate either a powder or a molded carrier substrate can be used.
- the amount of the metal amide supported in the composite is preferably 1 to 90% by mass, and more preferably 10 to 40% by mass.
- the composite is preferably prepared so that B/A is preferably 0.07 or more, more preferably 0.1 or more, and further preferably 0.2 or more, 0.3 or more, or 0.4 or more.
- the upper limit of B/A is preferably 2.3 or less, more preferably 2.0 or less, and further preferably 1.8 or less, 1.6 or less, or 1.5 or less.
- the active metal for use in the supported metal catalyst of the above (i) to (iii) is not particularly limited as long as it is a metal that has a catalytic activity in ammonia synthesis by direct reaction of hydrogen and nitrogen.
- Examples thereof include at least one of metals of the group 6, 7, 8, or 9 in the periodic table or a compound of the metal.
- metals of the group 6 in the periodic table include Cr, Mo, and W.
- metals of the group 7 in the periodic table include Mn, Tc, and Re.
- Examples of metals of the group 8 in the periodic table include Fe, Ru, and Os.
- metals of the group 9 in the periodic table include Co, Rh, and Ir.
- Ru is preferably used as an active metal in the supported metal catalyst of the above (i) to (iii).
- the amount of the active metal supported in the supported metal catalyst based on 100 parts by mass of the carrier is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, further preferably 0.03 parts by mass or more, 0.05 parts by mass or more, 0.1 parts by mass or more, 0.3 parts by mass or more, 0.5 parts by mass or more, or 1 part by mass or more.
- the upper limit of the amount of the active metal supported is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 15 parts by mass or less or 10 parts by mass or less. Note that the upper limit and the lower limit can be combined in any manner.
- the specific surface area of the supported metal catalyst is not particularly limited, and is preferably 0.1 to 250 m 2 /g and more preferably 0.5 to 200 m 2 /g.
- the specific surface area of the supported metal catalyst can be measured, for example, by a BET adsorption method.
- the supported metal catalyst can be prepared by a known method using the carrier and the active metal.
- a supported metal catalyst containing a conductive mayenite compound as a carrier can be prepared by a method described in WO 2012/077658 .
- ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12 is not limited to the supported metal catalysts of the above (i) to (iii) as long as it is an ammonia synthesis catalyst that is capable of synthesizing ammonia from nitrogen and hydrogen at a reaction pressure of 10 MPa or less.
- a supported ruthenium catalyst prepared using an oxide such as silicon oxide (silica), zinc oxide, aluminum oxide (alumina), magnesium oxide (magnesia), indium oxide, calcium oxide, zirconium oxide (zirconia), titanium oxide (titania), boron oxide, hafnium oxide, barium oxide, cerium oxide (ceria), or zeolite; a nitride, such as silicon nitride, aluminum nitride, boron nitride, or magnesium nitride; activated charcoal; or the like as a carrier can also be used.
- oxide such as silicon oxide (silica), zinc oxide, aluminum oxide (alumina), magnesium oxide (magnesia), indium oxide, calcium oxide, zirconium oxide (zirconia), titanium oxide (titania), boron oxide, hafnium oxide, barium oxide, cerium oxide (ceria), or zeolite
- a nitride such as silicon nitride, aluminum nitride, boro
- a supported metal catalyst prepared using a transition metal-supporting intermetallic compound obtained by supporting a transition metal on an intermetallic compound represented by the general formula A 5 X 3 (A represents a rare earth element and X represents Si or Ge) as described in WO 2017/111028 can be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- A represents a rare earth element and X represents Si or Ge
- a supported metal catalyst prepared using a transition metal-supporting intermetallic compound obtained by supporting a transition metal on Y 5 Si 3 is more preferred.
- a supported metal catalyst prepared using a three-dimensional intermetallic compound LaCoSi as described in Nature Catalysis, Vol. 1, March 2018, pp. 178-185 can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- a supported metal catalyst prepared using a mayenite compound produced by a hydrothermal synthesis method as described in WO 2018/030394 can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- a catalyst containing a Laves phase intermetallic compound that has a composition represented by the general formula ARu 2 (A represents one or more elements selected from Lanthanoid elements except for Y, Sc, or Ce) as an catalytically active component as described in WO 2017/047709 can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- A represents one or more elements selected from Lanthanoid elements except for Y, Sc, or Ce
- a catalyst containing YRu 2 as a catalytically active component is preferred.
- a supported metal catalyst prepared using an intermetallic compound LaScSi as described in Advanced Materials, 29, 1700924-1-7 (2017 ) can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- a supported metal catalyst prepared using an electride represented by the general formula LnH 2 (Ln represents La, Ce, Ca, or Y) as described in Inorganic Chemistry, Vol. 55, pp. 8833-8838 (2016 ) can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- an oxide-supported catalyst (Ru/La 0.5 Ce 0.5 O 1.75 ) in which ruthenium is supported as described in Chemical Science, Vol. 9, pp. 2230-2237 (2018 ) can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- a catalyst in which ruthenium is supported on praseodymium oxide as described in Chemical Science, Vol. 8, pp. 674-679 (2017 ) can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- an iron catalyst of a magnetite structure as described in Industrial & Engineering Chemistry, Vol. 18, pp. 1307-1309 (1926 ) can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- an iron catalyst of a Wustite structure as described in Applied Catalysis A, Vol. 142, pp. 209 (1996 ) can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- a catalyst in which ruthenium is supported on Celite (registered tradename) as described in Bulltin of the Chemical Society of Japan, Vol. 44, pp. 3216 (1971 ) can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- a catalyst in which ruthenium is supported on graphite as described in WO 84/03642 can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- a catalyst containing a cobalt-molybdenum composite nitride having cesium added thereto as described in Journal of Catalysis, Vol. 208, pp. 180-186 (2002 ) can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- a catalyst prepared using cobalt having barium added thereto as a supported metal and carbon as a carrier as described in ChemCatChem, Vol. 4, pp. 2836-2839 (2015 ) can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- a catalyst prepared using cobalt as a supported metal and using cerium oxide as a carrier as described in RSC Advances, Vol. 4, pp. 38093-38102 (2014 ) can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- an ammonia synthesis catalyst in which a carrier contains a perovskite oxide semiconductor as described in JP 2017-148810 A can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12.
- a supported metal catalyst containing a metal-supporting body in which a transition metal is supported on a cyanamide compound represented by the following general formula (1) as described in WO 2018/169076 can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12: MCN 2 (1) (wherein M represents an element of the group II in the periodic table).
- M is specifically at least one element selected from Be, Mg, Ca, Sr, and Ba, and among them, is preferably at least one element selected from Mg, Ca, Sr, and Ba. M is more preferably at least one element selected from Ca, Sr, and Ba since such a compound is not thermally decomposed and is stable even in a high temperature reaction condition. M is further preferably Ca since the atomic number is small so that the area per unit weight (specific surface area) is easily increased.
- the cyanamide compound is specifically a salt of a cyanamide (CN 2 H 2 ) and an element of the group II in the periodic table.
- a supported metal catalyst containing a transition metal-supporting body in which a transition metal is supported on an electron or hydride ion absorption-desorption material prepared using a lanthanoid oxyhydride represented by the following general formula (2) as described in WO 2019/176987 can also be used as the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12: Ln(HO) (2) (wherein, Ln represents a lanthanoid element).
- Ln is specifically at least one element selected from Gd, Sm, Pr, Ce, Er, Dy, Ho, La, and Nd.
- the transition metal is, for example, at least one metal selected from the group consisting of Ru, Fe, Co, Cr, and Mn.
- the ammonia synthesis catalyst used in the ammonia synthesis reactors 11 and 12 is preferably a supported metal catalyst prepared using a conductive mayenite compound, a supported metal catalyst prepared using a two-dimensional electride compound or a precursor compound thereof as a carrier, a supported metal catalyst prepared using a composite of a carrier substrate containing a metal oxide and a metal amide as a carrier, a supported metal catalyst prepared using a transition metal-supporting intermetallic compound obtained by supporting a transition metal on Y 5 Si 3 , a supported metal catalyst prepared using a three-dimensional intermetallic compound LaCoSi, a supported metal catalyst prepared using a mayenite compound produced by a hydrothermal synthesis method, a catalyst containing YRu 2 as a catalytically active component, a supported metal catalyst prepared using an intermetallic compound LaScSi, a supported metal catalyst prepared using an electride represented by the general
- one of the supported metal catalysts may be used alone or two or more thereof may be used in combination.
- the two or more supported metal catalysts may be mixed according to the reaction system, the supported metal catalysts may be laminated so that different layers are formed from type to type, or reaction tubes filled with different supported metal catalysts from type to type may be combined.
- the supported metal catalyst used in the ammonia synthesis reactor 11 and the supported metal catalyst used in the ammonia synthesis reactor 12 may be the same as or may be different from each other.
- an ammonia synthesis catalyst that provides an apparent activation energy of the ammonia synthesis reaction of preferably 80 kJ/mol or less, more preferably 60 kJ/mol or less is preferably used in the ammonia synthesis reactors 11 and 12.
- the apparent activation energy of the ammonia synthesis reaction can be calculated from the slope of a line obtained by plotting measurement results on an x-y plane with the ammonia production rate in the ammonia synthesis reaction on the y-axis and the reciprocal of the reaction temperature therein on the x-axis.
- the ammonia synthesis reaction pressure is 10 MPa or less, preferably 7 MPa or less, more preferably 5 MPa or less, and further preferably 3 MPa or less.
- An ammonia synthesis reaction pressure larger than 10 MPa leads to an increased energy required for compressing the raw material gases of the ammonia synthesis.
- the lower limit of the range of the ammonia synthesis reaction pressure is not particularly limited as long as ammonia can be synthesized while securing the ability to produce ammonia.
- the ammonia synthesis reaction pressure is preferably 500 kPa or more.
- the reaction pressure is a gage pressure (the same applies hereinafter).
- the upper limit and the lower limit may be combined in any manner.
- the ammonia synthesis reaction temperature is preferably 650°C or lower, more preferably 600°C or lower, further preferably 550°C or lower, and particularly preferably 530°C or lower.
- the ammonia synthesis reaction temperature preferably 100°C or higher, more preferably 200°C or higher, further preferably 250°C or higher, and particularly preferably 270°C or higher. Note that the upper limit and the lower limit may be combined in any manner.
- the ammonia synthesis reaction temperature is a temperature of the ammonia synthesis reaction that occurs inside the ammonia synthesis reactor and is different from the temperature of the inlet gas of the ammonia synthesis reactor.
- Ammonia is synthesized using an ammonia synthesis catalyst in the ammonia synthesis reactors 11 and 12.
- the method for adjusting the temperature of the catalyst may be selected, for example, from four choices in which either one of (i) a catalyst interlayer cooling system and (ii) a catalyst intralayer cooling system and either one of (iii) a cooled gas mixing system (gas quenching system) and (iv)a heat exchange system are combined.
- the system (i) is a system in which catalyst layers are divided into multiple stages and the reaction gas heated in a catalyst layer is cooled and then fed to the next catalyst layer.
- the system (ii) is a system in which the reaction gas is cooled in a catalyst layer.
- As a method for cooling the reaction gas there are the system (iii) in which a cold raw material gas is directly mixed with the reaction gas and the system (iv) in which a cooling tube is placed between layers to cool the reaction gas.
- the ammonia synthesis reactors 11 and 12 are preferably connected in series.
- the ammonia synthesis reactor 12 can synthesize ammonia using the ammonia-containing gas discharged from the ammonia synthesis reactor 11.
- the ammonia gas concentration in the ammonia-containing gas discharged from the ammonia synthesis reaction unit 10 can be further increased.
- the amount of the liquefied ammonia collected, which is separated by the gas-liquid separator 30, can be increased.
- the ammonia gas concentration in the circulated gas supplied to the ammonia synthesis reaction unit 10 can also be increased.
- the inlet gas temperature in each of the ammonia synthesis reactors 11 and 12 is preferably 100 to 600°C, more preferably 200 to 500°C, and further preferably 250 to 450°C.
- the inlet gas temperature is a temperature of the gas at an inlet (not shown) of the ammonia synthesis reactors 11 and 12.
- the ratio of hydrogen gas to nitrogen gas (H 2 /N 2 : molar ratio) in the inlet gas of each of ammonia synthesis reactors is preferably 0.5 to 4.0, more preferably 1.5 to 3.3, and further preferably 1.5 to 3.0.
- the ammonia synthesis reaction unit 10 may further include between the ammonia synthesis reactors 11 and 12 a heat exchanger 13 that cools the outlet gas of the ammonia synthesis reactor 11 so that the inlet gas temperature of the ammonia synthesis reactor 12 can be adjusted within the above range.
- the inlet gas temperature of the ammonia synthesis reactor 12 can be more easily adjusted within the above range and in addition, the heat generated by the ammonia synthesis reaction in the ammonia synthesis reactor 11 can be collected and efficiently used.
- the heat exchanger 13 is not particularly limited as long as another heat transfer medium can be heated with the heat of the outlet gas of the ammonia synthesis reactor 11.
- the heat exchanger 13 may heat the air fed by a blower with the heat of the outlet gas of the ammonia synthesis reactor 11 or may heat water to generate a high pressure steam.
- the cooling temperature in cooling the ammonia-containing gas can be increased.
- the cooling temperature in cooling the ammonia-containing gas in the gas-liquid separator 30 can be higher.
- the ammonia gas concentration of the circulated gas supplied to the ammonia synthesis reaction unit is 3% by volume or more, preferably 5% by volume or more, more preferably 6% by volume or more, and further preferably 7% by volume or more.
- the cooling temperature in cooling the ammonia-containing gas is to be lower for liquefying ammonia in the ammonia-containing gas, and the energy required in cooling the ammonia-containing gas is increased.
- the ammonia gas concentration in the circulated gas supplied to the ammonia synthesis reaction unit is preferably 35% by volume or less, and more preferably 25% by volume or less. Note that the upper limit and the lower limit may be combined in any manner.
- the ammonia gas concentration in the circulated gas supplied to the ammonia synthesis reaction unit 10 is the ammonia gas concentration in the circulated gas having added thereto the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supplying unit 40.
- the ammonia synthesis reaction pressure is in the above range and the ammonia gas concentration in the circulated gas supplied to the ammonia synthesis reaction unit 10 is in the above range, whereby the energy required for producing ammonia can be reduced while securing the ability to produce ammonia.
- the energy required for increasing the ammonia synthesis reaction pressure can be reduced.
- the cooling temperature of the ammonia-containing gas is to be decreased, and thus, the energy required for cooling the ammonia gas is even increased.
- the decrease in the cooling temperature of the ammonia-containing gas due to the ammonia synthesis reaction pressure in the above range can be suppressed.
- an increase in the energy required for cooling the ammonia-containing gas due to the ammonia synthesis reaction pressure in the above range can be suppressed.
- the energy required for increasing the ammonia synthesis reaction pressure is larger than the energy required for cooling the ammonia gas, as a result, the energy required for producing ammonia can be reduced.
- Ammonia synthesis in the ammonia synthesis reaction unit 10 will be described with reference to Fig. 2 .
- a circulated gas having an ammonia gas concentration of 4% by volume and a temperature of 300°C is supplied to the ammonia synthesis reactor 11 (point A).
- an ammonia synthesis reaction proceeds under a condition of a reaction pressure of 3 MPa to increase the ammonia concentration in the reaction gas. Since the ammonia synthesis reaction is an exothermal reaction, the reaction gas temperature is also increased.
- the ammonia concentration of the outlet gas of the ammonia synthesis reactor 11 is, for example, 9% by volume and the outlet gas temperature is, for example, 400°C (point B).
- the reaction gas discharged from the outlet of the ammonia synthesis reactor 11 is supplied to the ammonia synthesis reactor 12.
- the temperature is decreased while the ammonia concentration is maintained.
- the reaction gas temperature is decreased, for example, to 300°C (point C).
- the ammonia synthesis reaction proceeds under a condition of a reaction pressure of 3 MPa to increase the temperature of the reaction gas supplied to the ammonia synthesis reactor 12 again while further increasing the ammonia concentration in the reaction gas.
- the ammonia concentration of the reaction gas discharged from the outlet of the ammonia synthesis reactor 12 is, for example, 13% by volume
- the reaction gas temperature is a temperature lower than the temperature (point B) of the outlet gas of the ammonia synthesis reactor 11, for example, 350°C (point D).
- an ammonia-containing gas having an ammonia gas concentration of 13% by volume is synthesized from a circulated gas having an ammonia gas concentration of 4% by volume.
- the ammonia synthesis reactor 11 performs an ammonia synthesis reaction at a higher reaction temperature from the viewpoint of the reaction rate, and the ammonia synthesis reactor 12 performs an ammonia synthesis reaction at a lower reaction temperature from the viewpoint of the chemical equilibrium. Accordingly, the ammonia gas concentration in the ammonia-containing gas discharged from the ammonia synthesis reaction unit 10 can be higher.
- the ammonia cooler 20 cools the ammonia-containing gas which is discharged from the ammonia synthesis reaction unit 10 and which contains ammonia gas synthesized by the ammonia synthesis reaction unit 10.
- the ammonia gas synthesized by the ammonia synthesis reaction unit 10 can be liquefied and the liquefied ammonia can be collected by the gas-liquid separator 30.
- the ammonia cooler 20 cools the ammonia-containing gas, for example, through heat exchange by bringing the ammonia-containing gas into contact with a solid wall (mainly a metal wall) cooled with a heat transfer medium.
- the cooling temperature in cooling the ammonia-containing gas in the ammonia cooler 20 is preferably -40 to 15°C. Furthermore, from the viewpoint of capability of further reducing the pressure in liquefying the ammonia gas, the cooling temperature is more preferably -30 to 5°C.
- the ammonia cooler 20 preferably cools the ammonia-containing gas by heat exchange between a liquid having a boiling point at 1 atm of -33.0°C or higher and the ammonia-containing gas.
- the liquid used for cooling the ammonia-containing gas is preferably, for example, an anti-freezing fluid, and more preferably an alcohol-based brine containing an alcohol, such as ethylene glycol, propylene glycol, ethanol, or methanol.
- the gas-liquid separator 30 separates the liquefied ammonia produced from the ammonia-containing gas cooled by the ammonia cooler 20 from the circulated gas which contains unreacted nitrogen gas, unreacted hydrogen gas, and ammonia gas.
- the gas-liquid separator 30 is a device that separates and removes the liquefied ammonia associated with the circulated gas from the circulated gas.
- the gas-liquid separator 30 include a collision-type gas-liquid separator using a folded plate, a louver, or the like, a cyclone-type gas-liquid separator, a baffle-type gas-liquid separator, a bubble cap column, a packed column, and a wire mesh-type gas-liquid separator.
- the ammonia synthesizing gas supplying unit 40 supplies nitrogen gas and hydrogen gas to be added to the circulated gas.
- nitrogen gas and hydrogen gas consumed by the ammonia synthesis reaction can be replenished into the circulated gas.
- Nitrogen supplied by the ammonia synthesizing gas supplying unit 40 may be prepared by separating nitrogen from the air using a nitrogen separation membrane or a cryogenic separation process.
- nitrogen in the air used as an oxygen source may be used.
- the ammonia synthesizing gas supplying unit 40 can supply nitrogen from a nitrogen cylinder (including a nitrogen cylinder bundle, the same applies hereinafter) or a nitrogen tank (including a movable tank, such as nitrogen self-loader, the same applies hereinafter).
- Hydrogen supplied by the ammonia synthesizing gas supplying unit 40 can be prepared by a well-known method, for example, (i) a method in which hydrocarbon (for example, coal, petroleum, natural gas, and biomass) is converted into a gas containing CO and H 2 by a steam reforming reaction, a partial oxidation reaction, or a combination thereof, followed by a CO shift reaction and a decarbonation treatment, (ii) a method in which water is subjected to electrolysis, or (iii) a method in which water is decomposed using a photocatalyst.
- hydrocarbon for example, coal, petroleum, natural gas, and biomass
- the ammonia synthesizing gas supplying unit 40 may supply hydrogen from a hydrogen cylinder (including hydrogen cylinder bundle, the same applies hereinafter) or a hydrogen tank (including a movable tank, such as a hydrogen self-loader, the same applies hereinafter).
- a hydrogen cylinder including hydrogen cylinder bundle, the same applies hereinafter
- a hydrogen tank including a movable tank, such as a hydrogen self-loader, the same applies hereinafter.
- the ammonia synthesizing gas supplying unit 40 may further include a raw material gas production device that produces at least one of nitrogen gas and hydrogen gas.
- a raw material gas production device as described above, a known device may be used.
- the ammonia synthesizing gas supplying unit 40 may include a nitrogen cylinder or nitrogen tank for supplying nitrogen and may include a hydrogen cylinder or hydrogen tank for supplying hydrogen.
- the ammonia synthesis system 1 in an embodiment of the present invention may further include the ammonia synthesizing gas compressor 50 that compresses the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supplying unit 40 and the circulated gas compressor 60 that compresses the circulated gas separated by the gas-liquid separator 30.
- the reaction pressure in the ammonia synthesis and the pressure of the ammonia-containing gas in cooling the ammonia-containing gas can be further appropriately controlled.
- the ammonia synthesis system 1 further includes the ammonia synthesizing gas compressor 50, the amount of nitrogen gas and hydrogen gas added to the circulated gas can further be appropriately controlled.
- the ammonia synthesis system 1 further includes the circulated gas compressor 60, the circulated gas separated by the gas-liquid separator 30 can be recirculated at an economically appropriate space velocity.
- the ammonia synthesizing gas compressor 50 may compress each of nitrogen gas and hydrogen gas, or may compress a mixed gas obtained by mixing nitrogen gas and hydrogen gas.
- ammonia synthesis system 1 according to an embodiment of the present invention can be modified as follows.
- the number of the ammonia synthesizers 11 and 12 in the ammonia synthesis reaction unit 10 was two.
- the number of the ammonia synthesizers in the ammonia synthesis reaction unit is not limited to two, and may be one or may be three or more.
- the number of the ammonia synthesizers in the ammonia synthesis reaction unit 10 is preferably 2 to 5, more preferably 2 to 4, and further preferably 2 or 3.
- the outlet gas of the ammonia synthesizer 11 in the ammonia synthesis reaction unit 10 was cooled using the heat exchanger 13.
- the method for cooling the outlet gas of the ammonia synthesizer 11 is not limited to cooling by the heat exchanger 13.
- the outlet gas of the ammonia synthesizer 11 may be cooled by using the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supplying unit 40 as a quenching gas.
- the outlet gas of the ammonia synthesizer 11 may be cooled by using the circulated gas as a quenching gas.
- the outlet gas of the ammonia synthesizer 11 may be cooled by using the circulated gas having added thereto the nitrogen gas and hydrogen gas supplied from the ammonia synthesizing gas supplying unit 40 as a quenching gas.
- the position at which the cooling means is provided is not particularly limited as long as it is between the two or more ammonia synthesis reactors.
- the heat exchanger 13 may be provided between the ammonia synthesizer 11 and the ammonia synthesizer 12 with no heat exchanger provided between the ammonia synthesizer 12 and the ammonia synthesizer 14.
- the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supplying unit 40 were added to the circulated gas.
- the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supplying unit 40 may be added to the ammonia-containing gas.
- moisture and a miner amount of carbon dioxide contained in the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supplying unit 40 are transferred into the liquefied ammonia separated by the gas-liquid separator 30.
- the moisture and carbon dioxide contained in the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supplying unit 40 do not remain in the circulated gas supplied to the ammonia synthesis reaction unit 10. Accordingly, the moisture and carbon dioxide which are catalyst poisons can be removed from the gas used for the ammonia synthesis prior to the ammonia synthesis.
- the flow rate(s) of the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supplying unit 40 is(are) generally smaller than the flow rate of the ammonia-containing gas.
- the ammonia gas concentration in the ammonia-containing gas is not largely decreased.
- Modified Example 3 may be combined with Modified Example 2.
- the outlet gas of the ammonia synthesizer 11 may be cooled by using the circulated gas as a quenching gas.
- the outlet gas of the ammonia synthesizer 11 may be cooled by using the circulated gas having added thereto the nitrogen gas and hydrogen gas supplied from the ammonia synthesizing gas supplying unit 40 as a quenching gas.
- the circulated gas separated by the gas-liquid separator 30 may be supplied to the ammonia synthesis reaction unit 10 after heat exchange with the ammonia-containing gas using a heat exchanger 70. Since the temperature of the ammonia-containing gas is decreased by the heat exchange with the circulated gas, the driving energy of the cooler can be reduced.
- the ammonia-containing gas discharged from the ammonia synthesis reaction unit 10 may be subjected to heat exchange with the circulated gas to be supplied to the ammonia synthesis reaction unit 10 using a heat exchanger 80 before being supplied to the ammonia cooler 20. Since the temperature of the ammonia-containing gas is decreased by heat exchange with the circulated gas, the driving energy of the cooler can be reduced.
- ammonia synthesis system of the present invention is in no way to be limited to the ammonia synthesis system according to an embodiment of the present invention and the modified examples described above.
- ammonia synthesis system according to an embodiment of the present invention and the modified examples thereof can be combined and the modified examples can be combined.
- the method for producing ammonia of the present invention includes: an ammonia-containing gas production step of reacting nitrogen and hydrogen using an ammonia synthesis catalyst under a condition of a reaction pressure of 10 MPa or less to produce an ammonia-containing gas which contains ammonia gas; an ammonia-containing gas cooling step of cooling the ammonia-containing gas produced by the ammonia-containing gas production step; an ammonia separation step of separating ammonia liquefied by cooling of the ammonia-containing gas by the ammonia-containing gas cooling step from a circulated gas which contains unreacted nitrogen gas, unreacted hydrogen gas, and ammonia gas, to obtain liquefied ammonia; and an ammonia synthesizing gas supply step of supplying nitrogen gas and hydrogen gas to be added to at least one of the ammonia-containing gas and the circulated gas, the ammonia-containing gas production step being a step of reacting nitrogen and hydrogen using the circulated gas or the circulated gas having added thereto the nitrogen gas and hydrogen gas supplied by the ammoni
- ammonia-containing gas production step nitrogen and hydrogen are reacted using an ammonia synthesis catalyst under a condition of a reaction pressure of 10 MPa or less to produce an ammonia-containing gas which contains ammonia gas. Then, nitrogen and hydrogen are reacted using the circulated gas or the circulated gas having added thereto the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supply step.
- ammonia synthesis catalyst used in the ammonia-containing gas production step the reaction pressure and reaction temperature in the ammonia synthesis reaction, and the ammonia gas concentration in the circulated gas are the same as those described above in the ammonia synthesis reaction unit of the ammonia synthesis system according to an embodiment of the present invention, and thus, the explanations of the ammonia synthesis catalyst used in the ammonia-containing gas production step, the reaction pressure and reaction temperature in the ammonia synthesis reaction, and the ammonia gas concentration in the circulated gas are omitted.
- the ammonia-containing gas production step preferably includes a first ammonia-containing gas production step and a second ammonia-containing gas production step as described below.
- first ammonia-containing gas production step nitrogen and hydrogen are reacted using the circulated gas or the circulated gas having added thereto the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supply step and using an ammonia synthesis catalyst to produce a first ammonia-containing gas which contains ammonia gas.
- second ammonia-containing gas production step nitrogen and hydrogen are reacted using the first ammonia-containing gas production step and the first ammonia-containing gas and using an ammonia synthesis catalyst to produce a second ammonia-containing gas which contains ammonia gas at a concentration higher than in the first ammonia-containing gas.
- ammonia gas concentration in the ammonia-containing gas produced in the ammonia-containing gas production step can be further increased.
- the first ammonia-containing gas production step is the same as the ammonia synthesis in the ammonia synthesis reactor 11 of the ammonia synthesis reaction unit 10 in the ammonia synthesis system 1 according to an embodiment of the present invention.
- the second ammonia-containing gas production step is the same as the ammonia synthesis in the ammonia synthesis reactor 12 of the ammonia synthesis reaction unit 10 in the ammonia synthesis system 1 according to an embodiment of the present invention.
- the explanations of the first ammonia-containing gas production step and the second ammonia-containing gas production step are omitted.
- the temperature of the circulated gas or the circulated gas having added thereto the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supply step used in the first ammonia-containing gas production step and the temperature of the first ammonia-containing gas used in the second ammonia-containing gas production step are each preferably 100 to 600°C, more preferably 200 to 500°C, and further preferably 250 to 450°C.
- the circulated gas or the circulated gas having added thereto the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supply step used in the first ammonia-containing gas production step and the first ammonia-containing gas used in the second ammonia-containing gas production step each have a ratio of hydrogen gas to nitrogen gas (H 2 /N 2 : molar ratio) of preferably 0.5 to 4.0, more preferably 1.5 to 3.3, and further preferably 1.5 to 3.0.
- the ammonia-containing gas production step may include a first ammonia-containing gas cooling step of cooling the first ammonia-containing gas by heat exchange. Then, in the second ammonia-containing gas production step, the second ammonia-containing gas may be produced by using the first ammonia-containing gas cooled by the first ammonia-containing gas cooling step.
- the first ammonia-containing gas cooling step is the same as the cooling of the outlet gas of the ammonia synthesis reactor 11 by the heat exchanger 13 of the ammonia synthesis reaction unit 10 in the ammonia synthesis system 1 according to an embodiment of the present invention, and thus, the explanation of the first ammonia-containing gas cooling step is omitted.
- the ammonia-containing gas production step may include a first ammonia-containing gas cooling step of cooling the first ammonia-containing gas by using at least either of the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supply step or the circulated gas. Then, in the second ammonia-containing gas production step, the second ammonia-containing gas may be produced by using the first ammonia-containing gas cooled by the first ammonia-containing gas cooling step.
- the first ammonia-containing gas cooling step is the same as the cooling of the outlet gas of the ammonia synthesis reactor 11 in Modified Example 2 of the ammonia synthesis system 1 according to an embodiment of the present invention, and thus, the explanation of the first ammonia-containing gas cooling step is omitted.
- the ammonia-containing gas cooling step the ammonia-containing gas produced by the ammonia-containing gas production step is cooled.
- the ammonia-containing gas cooling step is the same as the cooling of the ammonia-containing gas by the ammonia cooler 20 in the ammonia synthesis system 1 according to an embodiment of the present invention, and thus, the explanation of the ammonia-containing gas cooling step is omitted.
- ammonia separation step ammonia liquefied by cooling of the ammonia-containing gas by the ammonia-containing gas cooling step is separated from the circulated gas which contains unreacted nitrogen gas, unreacted hydrogen gas, and ammonia gas to obtain liquefied ammonia.
- the ammonia separation step is the same as the separation of the circulated gas by the gas-liquid separator 30 in the ammonia synthesis system 1 according to an embodiment of the present invention, and thus, the explanation of the ammonia separation step is omitted.
- ammonia synthesizing gas supply step nitrogen gas and hydrogen gas to be added to at least one of the ammonia-containing gas and the circulated gas are supplied.
- the ammonia synthesizing gas supply step is the same as the supply of nitrogen gas and hydrogen gas by the ammonia synthesizing gas supplying unit 40 in the ammonia synthesis system 1 according to an embodiment of the present invention, and thus, the explanation of the ammonia synthesizing gas supply step is omitted.
- the method for producing ammonia of the present invention may further include an ammonia synthesizing gas compression step of compressing the nitrogen gas and hydrogen gas supplied by the ammonia synthesizing gas supply step and a circulated gas compression step of compressing the circulated gas separated in the ammonia-containing gas cooling step.
- the ammonia synthesizing gas compression step and the circulated gas compression step are respectively the same as the compression of nitrogen gas and hydrogen gas by the ammonia synthesizing gas compressor 50 and the compression of the circulated gas by the circulated gas compressor in the ammonia synthesis system 1 according to an embodiment of the present invention, and thus, the explanations of the ammonia synthesizing gas compression step and the circulated gas compression step are omitted.
- Ammonia synthesis was simulated under the conditions shown in Table 1 and the conditions described below to determine the power of gas compressors that consume the largest power in the ammonia synthesis system.
- the system configuration used in the simulation is shown in Fig. 12 .
- the ammonia gas concentration in the circulated gas supplied to the ammonia synthesis reaction unit in the ammonia synthesis system according to an embodiment of the present invention corresponds to the ammonia concentration in S403 in the ammonia synthesis system shown in Fig. 12 .
- Fig.1 in Angewandte Chemie International Edition, 2018, Vol. 57, pp. 2648-2652 shows that an Ru/Ba-Ca(NH 2 ) 2 catalyst (a supported metal catalyst prepared using a composite of a carrier substrate containing a metal oxide and a metal amide as a carrier), a Cs-Ru/MgO catalyst, and an Fe catalyst (an iron catalyst of the Wustite structure) have a high activity at a pressure of 0.9 MPa and at a temperature of 300 to 400°C.
- the results of the following simulation can be reproduced in a practical ammonia synthesis system.
- the ammonia synthesis catalysts described in the section of "Ammonia synthesis catalyst” above also have a high catalytic activity under a low temperature and a low pressure, and thus, the ammonia synthesis catalysts can be used to reproduce the results of the following simulation in a practical ammonia synthesis system.
- the simulation was performed with a raw material hydrogen supplying pressure of 3.3 MPa, a nitrogen supplying pressure of 0.7 MPa, a pressure increase range of the circulated gas compressor of 0.3 MPa, and an efficiency of the compressor of 80%.
- Table 1 shows the evaluation results of the powers of the gas compressors by the simulation.
- Table 1 Unit Example 1
- Example 2 Example 3
- Example 4 Example 5 Comparative Example 1 Comparative Example 2
- Reaction pressure in ammonia synthesis reaction (R401) (R402) MPa 3 3 3 5 7 25 12 NH 3 concentration (S403) % by volume 3.1 5.5 7.1 8.2 9.2 7.1 1.9
- Temperature of NH 3 synthesis reactor inlet gas (R401) (R402) °C 400 350 300 300 250 300 300
- Amount of NH 3 synthesis reactor inlet gas (S403) Nm 3 /h 9.8 ⁇ 10 4 7.2 ⁇ 10 4 4.7 ⁇ 10 4 3.7 ⁇ 10 4 2.4 ⁇ 10 4 4.7 ⁇ 10 4 2.1 ⁇ 10 4
- Raw material gas compressors total of C201, C202, C301, C302, C303) kW
- the results of the above simulation can also be reproduced by using any of the catalysts described in the section “Ammonia synthesis catalyst”.
- the catalysts described in the section “Ammonia synthesis catalyst” from the viewpoint of a high catalytic activity under the conditions of the simulation, in other words, from the viewpoint of having a high catalytic activity even at a low temperature, the catalysts mentioned as preferred catalysts in the section “Ammonia synthesis catalyst” are preferred also as an ammonia synthesis catalyst that reproduces the simulation results.
- Comparative Example 1 As can be seen from Comparative Example 1, it was found that when ammonia gas containing unreacted gases was cooled with a temperature of 30°C as in the ammonia synthesis system described in PTL 1, for securing the ability to produce ammonia of 20,000 ton/year, the reaction pressure in the ammonia synthesis reaction was to be 25 MPa which is much larger than 10 MPa, and thus, the power of gas compressors which consume the largest power in the ammonia synthesis system was increased.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018198952 | 2018-10-23 | ||
PCT/JP2019/041370 WO2020085324A1 (fr) | 2018-10-23 | 2019-10-21 | Système de synthèse d'ammoniac et procédé de production d'ammoniac |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3872036A1 true EP3872036A1 (fr) | 2021-09-01 |
EP3872036A4 EP3872036A4 (fr) | 2022-07-20 |
Family
ID=70331420
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19876356.7A Pending EP3872036A4 (fr) | 2018-10-23 | 2019-10-21 | Système de synthèse d'ammoniac et procédé de production d'ammoniac |
Country Status (5)
Country | Link |
---|---|
US (1) | US20210380426A1 (fr) |
EP (1) | EP3872036A4 (fr) |
JP (2) | JP7374705B2 (fr) |
CN (1) | CN112996751A (fr) |
WO (1) | WO2020085324A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210380426A1 (en) * | 2018-10-23 | 2021-12-09 | Tsubame Bhb Co., Ltd. | Ammonia synthesis system and ammonia production method |
CN115744933B (zh) * | 2022-11-10 | 2024-02-06 | 中国华能集团清洁能源技术研究院有限公司 | 一种绿氨生产系统及方法 |
WO2024122228A1 (fr) * | 2022-12-05 | 2024-06-13 | 株式会社豊田中央研究所 | Système de synthèse de l'ammoniac |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3350170A (en) * | 1965-10-29 | 1967-10-31 | Pullman Inc | Process for carrying out cyclic synthesis reactions at elevated pressures |
GB1601475A (en) * | 1977-04-18 | 1981-10-28 | Ici Ltd | Catalytic reactor |
EP0011404B1 (fr) * | 1978-11-10 | 1982-12-29 | Imperial Chemical Industries Plc | Procédé pour la fabrication intégrée de méthanol et d'ammoniaque |
GB8307612D0 (en) | 1983-03-18 | 1983-04-27 | British Petroleum Co Plc | Ammonia production and catalysts |
GB8410517D0 (en) | 1984-04-25 | 1984-05-31 | Ici Plc | Ammonia synthesis |
NL8402090A (nl) * | 1984-06-30 | 1986-01-16 | Stamicarbon | Werkwijze voor de bereiding van ammoniak. |
US4568530A (en) * | 1984-10-16 | 1986-02-04 | The M. W. Kellogg Company | Ammonia synthesis |
CA2004216A1 (fr) * | 1988-11-30 | 1990-05-31 | Joseph D. Korchnak | Production d'ammoniac a partir de charge d'alimentation hydrocarbonee |
NL1013016C2 (nl) * | 1999-09-10 | 2001-03-13 | Continental Engineering B V | Werkwijze en inrichting voor het bereiden van ammoniak in een kringloopstroom onder toepassing van keramische membranen. |
DE10057863C2 (de) * | 2000-11-21 | 2002-10-24 | Uhde Gmbh | Mehrdruckverfahren zur Herstellung von Ammoniak |
US7371361B2 (en) * | 2004-11-03 | 2008-05-13 | Kellogg Brown & Root Llc | Maximum reaction rate converter system for exothermic reactions |
JP5373410B2 (ja) * | 2009-01-09 | 2013-12-18 | トヨタ自動車株式会社 | アンモニア合成方法 |
EP2374758A1 (fr) * | 2010-04-07 | 2011-10-12 | Ammonia Casale S.A. | Récupération d'hydrogène et d'azote pour gaz de purge d'ammoniac |
JP2011246311A (ja) * | 2010-05-28 | 2011-12-08 | Nippon Shokubai Co Ltd | アンモニア合成方法 |
US9150423B2 (en) | 2010-12-07 | 2015-10-06 | Tokyo Institute Of Technology | Ammonia synthesis catalyst and ammonia synthesis method |
CN102815722B (zh) * | 2011-06-10 | 2014-08-06 | 中国石油天然气股份有限公司 | 铁催化剂串钌催化剂氨合成工艺 |
CN202519043U (zh) * | 2012-05-10 | 2012-11-07 | 毕节金河化工有限公司 | 一种合成氨装置 |
JP5884101B2 (ja) | 2012-07-26 | 2016-03-15 | 国立大学法人東京工業大学 | 窒化物エレクトライド及びその製法 |
JP6399867B2 (ja) | 2014-09-05 | 2018-10-03 | 三菱重工エンジニアリング株式会社 | アンモニア合成システム及び方法 |
JP2016141599A (ja) * | 2015-02-02 | 2016-08-08 | 味の素株式会社 | 液化アンモニアの製造システム及び製造方法 |
WO2017047709A1 (fr) | 2015-09-15 | 2017-03-23 | 国立大学法人東京工業大学 | Composé intermétallique à phase de laves, catalyseur utilisant le composé intermétallique, et procédé de production d'ammoniac |
CN108472632A (zh) | 2015-12-25 | 2018-08-31 | 国立研究开发法人科学技术振兴机构 | 过渡金属担载金属间化合物、担载金属催化剂以及氨的制造方法 |
AU2016395665B2 (en) | 2016-03-03 | 2019-07-11 | Jgc Corporation | Ammonia production method |
EP3257814A1 (fr) * | 2016-06-17 | 2017-12-20 | Casale SA | Procédé pour la production d'ammoniac |
WO2018030394A1 (fr) | 2016-08-08 | 2018-02-15 | 国立大学法人東京工業大学 | Procédé de fabrication d'un catalyseur de synthèse d'ammoniac, et procédé de fabrication d'ammoniac |
US11819827B2 (en) | 2017-03-17 | 2023-11-21 | Japan Science And Technology Agency | Supported metal material, supported metal catalyst, method of producing ammonia, method of producing hydrogen and method of producing cyanamide compound |
JP6388417B2 (ja) | 2017-05-26 | 2018-09-12 | 住友化学株式会社 | アンモニア合成触媒及びアンモニアの製造方法 |
WO2019176987A1 (fr) | 2018-03-14 | 2019-09-19 | 国立研究開発法人科学技術振興機構 | Matériau absorbant/désorbant d'électrons ou d'ions hydrures, composition absorbante/désorbante d'électrons ou d'ions hydrures, support de métal de transition et catalyseur, et leur utilisation |
JP7103155B2 (ja) * | 2018-10-22 | 2022-07-20 | 日本製鉄株式会社 | 高炉操業方法 |
US20210380426A1 (en) * | 2018-10-23 | 2021-12-09 | Tsubame Bhb Co., Ltd. | Ammonia synthesis system and ammonia production method |
-
2019
- 2019-10-21 US US17/287,025 patent/US20210380426A1/en active Pending
- 2019-10-21 EP EP19876356.7A patent/EP3872036A4/fr active Pending
- 2019-10-21 JP JP2019191952A patent/JP7374705B2/ja active Active
- 2019-10-21 WO PCT/JP2019/041370 patent/WO2020085324A1/fr active Search and Examination
- 2019-10-21 JP JP2020553403A patent/JP7374920B2/ja active Active
- 2019-10-21 CN CN201980070116.3A patent/CN112996751A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
WO2020085324A1 (fr) | 2020-04-30 |
JPWO2020085324A1 (ja) | 2021-10-07 |
CN112996751A (zh) | 2021-06-18 |
JP2020066573A (ja) | 2020-04-30 |
US20210380426A1 (en) | 2021-12-09 |
JP7374920B2 (ja) | 2023-11-07 |
EP3872036A4 (fr) | 2022-07-20 |
JP7374705B2 (ja) | 2023-11-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6680919B2 (ja) | 担持金属触媒 | |
EP3872036A1 (fr) | Système de synthèse d'ammoniac et procédé de production d'ammoniac | |
EP3967783A1 (fr) | Catalyseur de déshydrogénation de matières premières de stockage d'hydrogène organiques, support du catalyseur, alliage de stockage d'hydrogène et procédé de fourniture d'hydrogène de haute pureté | |
US10017395B2 (en) | Ammonia synthesis catalyst and ammonia synthesis method | |
EP3967396A1 (fr) | Catalyseur pour déshydrogéner un matériau brut de stockage d'hydrogène organique, support pour catalyseur, alliage de stockage d'hydrogène et procédé pour fournir de l'hydrogène de haute pureté | |
JP5820817B2 (ja) | アンモニア合成触媒及びアンモニア合成方法 | |
ES2728916T3 (es) | Procedimiento para hacer funcionar un reactor HTS con relación molar O/C baja | |
US11866342B2 (en) | Composite oxide, metal-supported material, and ammonia synthesis catalyst | |
EP3228386A1 (fr) | Corps composite, procédé pour la production de corps composite, catalyseur de synthèse d'ammoniac et procédé de synthèse d'ammoniac | |
CN112041271B (zh) | 复合氧化物、金属担载物以及氨合成催化剂 | |
Ni et al. | Effect of rare earth on the performance of Ru/MgAl-LDO catalysts for ammonia synthesis | |
US11795062B2 (en) | Electron or hydride ion intake/release material, electron or hydride ion intake/release composition, transition metal-supported material and catalyst, and use in relation thereto | |
Vereshchagin et al. | New method for regulating the activity of ABO 3 perovskite catalysts | |
Tao et al. | Highly selective and stable ZrO 2–Al 2 O 3 for synthesis of dimethyl carbonate in reactive distillation | |
US10695751B2 (en) | Laves phase intermetallic compound, catalyst using intermetallic compound, and method for producing ammonia | |
US20230140129A1 (en) | Thermal battery | |
Pinzón et al. | Perovskites as Catalyst Precursor for Hydrogen Production from Ammonia Decomposition | |
EP4129472A1 (fr) | Micro-catalyseur de nickel, son procédé de préparation et son utilisation | |
Reina et al. | Influence of the Lanthanide Oxides on the Catalytic Behavior of Au/Al2O3 Catalysts for Total and Preferential CO Oxidation | |
KR20240095693A (ko) | 암모니아 분해용 촉매 및 이의 제조방법 | |
JP2020142189A (ja) | アンモニア合成用触媒 | |
JP2023542439A (ja) | アンモニア分解反応のための合金/酸化物、合金/窒化物複合触媒 | |
CN116351418A (zh) | 一种用于非热等离子体制氨的催化剂及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20210420 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
A4 | Supplementary search report drawn up and despatched |
Effective date: 20220621 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C01C 1/12 20060101ALI20220614BHEP Ipc: C01C 1/04 20060101AFI20220614BHEP |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20231206 |
|
TPAC | Observations filed by third parties |
Free format text: ORIGINAL CODE: EPIDOSNTIPA |